Vertically Integrated Pure Lithium Metal Production and Lithium Battery Production

ABSTRACT

Methods are proposed for fabricating highly pure lithium metal electrodes from aqueous lithium salt solutions by means of electrolysis through lithium ion selective membranes, performed at constant current densities between about 10 mA/cm 2  and about 50 mA/cm 2 , and wherein the constant current is applied for a time between about 1 minute and about 60 minutes. The electrolysis is performed under a blanketing atmosphere, the blanketing atmosphere being substantially free of lithium reactive components. Methods are further proposed for vertically integrating the electrolytic fabrication of highly pure lithium metal electrodes into the production of lithium metal batteries, the fabrication of lithium electrodes and lithium metal batteries being performed in a single facility.

CROSS-REFERENCE TO RELATED APPLICATIONS

Related application filed on the same date as the present applicationand having the same inventor and same assignee as the presentapplication, entitled “Lithium Metal Anode and Battery” and havingassigned application Ser. No. 17/006,048 is hereby incorporated byreference.

TECHNICAL FIELD

The present invention relates to the production of highly pure lithiumfor use in lithium metal batteries, and the integration of lithium metalproduction with the production of Li batteries. The resultant batteriesare manufactured in a fully charged state, and have increased cycle lifecompared to conventional manufacturing methods.

BACKGROUND ART

Lithium ion batteries (LIBs) dominate the lithium battery market. LIBscontain lithium which is only present in an ionic form. Such batterieshave good charging density and can function effectively through multiplecharge/discharge cycles. Lithium metal batteries (LMBs) by contrast, usenon-ionic lithium metal at the negative electrode. During discharge ofan LMB, lithium ions are released from this electrode, as electrons flowthrough an external circuit. As the LMB recharges, lithium ions arereduced back to lithium metal as electrons flow back into the negativeelectrode. Because LMBs have intrinsically higher capacity than LIBs,they are the preferred technology for primary batteries. Moreover, sinceLMBs can be manufactured in the fully charged state, they do not requirethe lengthy formation process needed for LIBs, which can take between20-30 days. However, poor cycle life, volumetric expansion, and thetendency to form lithium metal dendrites, which can lead to violentcombustion of LMBs, have limited their practical use as rechargeablebatteries.

Lithium anodes in rechargeable lithium metal batteries (LMBs) areconsidered the “Holy Grail” of anode materials due to their remarkablyhigh theoretical specific capacity of 3860 mAh/g and low reactionvoltage. Lithium metal is the lightest metal on the periodic table, andit is especially desired for applications that require a low ratio ofvolume to weight, such as electric vehicles. The most promising LMB'sare Lithium Sulfur (Li—S), Lithium Air (Li—O₂), and Solid-State orSemi-Solid LMB's. While primary batteries manufactured with lithiummetal foils are widely commercialized, numerous barriers to thecommercialization of rechargeable LMB's include low Coulombicefficiency, poor cycle life, soft shorts, volumetric expansion and thegrowth of Li dendrites during plating—which can lead to thermal runawayand other catastrophic failures. Tremendous efforts have been made tosuppress dendrite formation including by providing additives inelectrolytes, varying the salt concentration, creating artificialpassivating layers on lithium metal (allowing one to handle lithiummetal in dry air for a brief amount of time, but at the cost of higherimpedance), and manipulating electrode-electrolyte interfacialstructure—which is extremely difficult to do when a foil is mechanicallyfused to a substrate to create a negative electrode, and that negativeelectrode is then mechanically fused to a solid-state electrolyte.

Other barriers include the quality and cost of available lithium metalraw material, handling of lithium metal, and the mechanical challengesof manufacturing a lithium anode. These barriers increase by orders ofmagnitude when attempting to mechanically manufacture a solid-state LMB.Since 1976, researchers—including Nobel Prize winners—have attempted tosolve all these problems to no avail. It is 2020 and the absence of acommercially viable battery for consumer applications—despite theefforts of the best minds in the field—is stinging.

The current commercially available supply of lithium metal is producedby molten salt electrolysis of lithium chloride. Lithium is poured intoa mold and extruded into foils that range in thickness from 100 μm-750μm. For environmental reasons, lithium metal foils are generallyproduced in China. Because of lithium's classification as a flammableand potentially explosive material, these foils must then be shippedunder mineral oil to a battery manufacturer. The process yields animpure foil that, under scanning electron microscope (SEM) imaging,appears intrinsically dendritic, with an uneven surface that can vary by+/−50 μm (U.S. Pat. No. 10,177,366, FIG. 11A). The resulting impureproduct, while sufficient for primary lithium batteries, is not usablein rechargeable LMB's.

Shipping and handling, and the required immersion in mineral oilcompromise the integrity of the lithium metal. Prior to use inbatteries, the mineral oil must be removed, which further compromisesthe lithium. Some battery developers manually scrape lithium from underthe top layer to use and spread it on the copper or other substrate likepeanut butter. Some take the lithium metal foil, and vapor deposit itonto a substrate, which is both expensive and energy intensive.

Impurities in the present supply of lithium metal foil provide anadditional barrier to the commercialization of LMB's. As an alkalimetal, lithium has one loosely held valence electron, causing it to beinherently reactive. Notably, lithium is the only alkali metal thatreacts with nitrogen in the air, forming the nitride Li₃N. Due toundesirable side-reactions, the introduction of impurities into thelithium foil severely limits the operation of a working battery. Inparticular, a recent study found that such impurities can lead to thenucleation of sub-surface dendritic structures. (Harry et al., Nat.Mater. 13, 69-73 (2014)). The manufacturer of the lithium foil in thestudy (FMC Lithium) listed a number of elements other than lithium, themost abundant at a concentration of 300 ppm by weight is nitrogen,likely in the form of Li₃N. (U.S. Pat. No. 4,781,756). Other commonimpurities include: Na, Ca, K, Fe, Si, Cl, B, Ti, Mg and C. While thisis not an exhaustive list, the elements mentioned are the most common.Nitrogen in any form is particularly undesirable in rechargeable LMBs.Nitrogen forms voids and pits in the lithium metal as a battery cyclesand also consumes lithium with these reactions. The presence ofimpurities such as nitrogen leads to slowed and uneven lithiumdeposition on a negative electrode during charging, affecting theoverall current distribution in the battery and creating hot spots.

The unevenness of the lithium foil surface caused by nitrogen and otherimpurities is also highly problematic because it prevents uniformcontact of the substrate with the electrode, leading to soft shorts andagain, uneven distribution of current, which in turn can lead todendrites and other undesirable effects.

A method is needed to provide a pure lithium metal anode, whichovercomes the purity issues heretofore limiting the capacity andrecycling life of LMBs.

SUMMARY OF THE EMBODIMENTS

While the general approach is to suppress all the problems inherent inthe existing supply of raw material, an approach which has not beensuccessful in over forty-three years, the inventor proposes to addressthe materials problem and the manufacturing problem simultaneously byproducing a highly improved lithium metal product (a full negativeelectrode) and vertically integrating lithium metal production intobattery manufacturing facilities.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium electrode is described, the method including thesteps of:

(1) providing an electrolytic cell, the electrolytic cell including:

-   -   a first chamber containing a positive electrode, and an aqueous        lithium salt solution in contact with the positive electrode;    -   a second chamber containing a conductive substrate configured as        a negative electrode, the conductive substrate being stationary        in the chamber during lithium metal electrodeposition, a lithium        ion-selective membrane separating the first chamber from the        second chamber, and a non-aqueous electrolyte disposed between        the conductive substrate and the lithium ion selective membrane,        physically contacting both the conductive substrate and the        lithium ion selective membrane;    -   the electrolytic cell being configured to allow passage of        lithium ions through the lithium ion selective membrane between        the first and the second chambers, and to preclude the passage        of other chemical species between the first and the second        chambers;

(2) blanketing the electrolytic cell with a blanketing atmosphere, theblanketing atmosphere being substantially free of lithium reactivecomponents;

(3) applying a variable voltage in order to maintain a constant currentacross the negative electrode and the positive electrode, therebycausing lithium ions to cross from the first chamber to the secondchamber, through the lithium ion selective membrane and the non-aqueouselectrolyte, and electrodeposit a first layer of lithium onto theconductive substrate, thereby forming the lithium electrode, the firstlayer of lithium having an inner face and an outer face, the inner faceof the first layer of lithium bonded to the conductive substrate;

wherein the constant current is between about 10 mA/cm² and about 50mA/cm², and wherein the constant current is applied for a time betweenabout 1 minute and about 60 minutes.

According to some embodiments, the blanketing atmosphere includes nomore than 10 ppm of lithium reactive components on a molar basis. Insome embodiments the blanketing atmosphere includes no more than 10 ppmnitrogen on a molar basis. In some embodiments, the blanketingatmosphere includes no more than 5 ppm nitrogen on a molar basis.

According to some embodiments, the conductive substrate comprises aplate having a first face and a second face, wherein the inner face ofthe first layer of lithium metal bonds to the first face of theconductive substrate.

According to some embodiments, the aqueous lithium salt solutioncomprises a lithium salt selected from the group consisting of L₂SO₄,Li₂CO₃, and combinations thereof. In a preferred embodiment, the aqueouslithium salt solution includes Li₂SO₄.

According to some embodiments, the conductive substrate is selected froma group consisting of copper, aluminum, graphite coated copper, andnickel.

According to some embodiments, the lithium ion selective membraneincludes a polymeric matrix and a plurality of ion-conducting particlesdisposed within the polymeric matrix. In some embodiments, the lithiumion selective membrane comprises a glass frit with lithium ionconducting particles disposed within. According to some embodiments, theblanketing atmosphere comprises argon with a purity of greater than99.998 weight percent. According to some embodiments, the lithiumelectrode has a specific capacity of greater than about 3800 mAh pergram of lithium.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium electrode is described, the method including thesteps of:

(1) providing a gas-impermeable container, the container enclosing:

-   -   a blanketing atmosphere, the blanketing atmosphere being        substantially free of lithium reactive components;    -   an electrolytic cell, the electrolytic cell being blanketed        completely by the blanketing atmosphere, and including:        -   a conductive substrate, stationary within the cell,            configured as a negative electrode;        -   a positive electrode;        -   an aqueous lithium salt solution interposed between the            conductive substrate and the positive electrode;        -   a lithium ion-selective membrane configured to function as a            solid state electrolyte, covering the conductive substrate,            and forming a barrier separating the aqueous lithium salt            solution and the conductive substrate;    -   the electrolytic cell being configured to allow passage of        lithium ions from the lithium salt solution through the lithium        ion selective membrane and onto the surface of the conductive        substrate, and to preclude the passage of other chemical        species;

(2) applying a variable voltage in order to maintain a constant currentacross the negative electrode and the positive electrode, therebycausing lithium ions to cross from the lithium salt solution through thelithium ion selective membrane, and electroplate a layer of lithium ontothe conductive substrate, thereby forming the lithium electrode, thelayer of lithium having an inner face and an outer face, the inner facebonding to the conductive substrate and the outer face bonding to thelithium ion-selective membrane;

-   -   wherein the constant current is between about 10 mA/cm² and        about 50 mA/cm², and wherein the constant current is applied for        a time between about 1 minute and about 60 minutes.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium metal battery is described, comprising:

(1) manufacturing a lithium electrode according to methods of theinstant invention;

(2) assembling a casing with contents including the lithium electrodeconfigured as an anode, and other components necessary to form thelithium metal battery;

(3) sealing the casing to isolate the contents of the casing fromreactants present in the air, thereby providing the lithium metalbattery.

In preferred embodiments, LIMBs are fabricated in a single manufacturingfacility. In some embodiments, all steps of battery manufacture areperformed under a blanketing atmosphere substantially free of lithiumreactive components.

In some embodiments the lithium metal battery is fabricated with alithium metal electrode having a layer of lithium metal bonded to theconductive substrate, wherein the layer of lithium metal includes nomore tha 5 ppm of non-metallic elements by mass.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium metal battery is described, comprising:

(1) providing an electrolytic cell, the electrolytic cell including:

-   -   a conductive substrate, stationary within the electrolytic cell,        the conductive substrate comprising a plate having a first face        and a second face;    -   a first chamber containing a first positive electrode, and a        first aqueous lithium salt solution in contact with the first        positive electrode;    -   a second chamber containing a first lithium ion-selective        membrane separating the first chamber from the second chamber,        and a first non-aqueous electrolyte disposed between the first        face of the conductive substrate and the first lithium ion        selective membrane, physically contacting both the first face of        the conductive substrate and the lithium ion selective membrane;    -   a third chamber containing a second lithium ion-selective        membrane and a non-aqueous electrolyte disposed between the        second face of the conductive substrate and the second lithium        ion selective membrane, physically contacting both the second        face of the conductive substrate and the second lithium ion        selective membrane;    -   a fourth chamber containing a second positive electrode, and a        second aqueous lithium salt solution in contact with the second        positive electrode;    -   the second lithium ion-selective membrane separating the third        chamber from the fourth chamber;    -   the electrolytic cell being configured to allow passage of        lithium ions through the first lithium ion selective membrane        between the first and the second chambers, and to preclude the        passage of other chemical species between the first and the        second chambers;    -   the electrolytic cell being configured to allow passage of        lithium ions through the second lithium ion selective membrane        between the fourth and the third chambers, and to preclude the        passage of other chemical species between the fourth and the        third chambers;

(2) blanketing completely the electrolytic cell with a blanketingatmosphere, the blanketing atmosphere being inert to chemical reactionwith lithium;

(3) applying a variable voltage in order to maintain a constant currentacross the conductive substrate and the first positive electrode, andacross the conductive substrate and the second positive electrode,thereby causing lithium ions to cross from the first chamber to thesecond chamber, through the first lithium ion selective membrane and thefirst non-aqueous electrolyte, and electroplate a first layer of lithiumonto the first face of the conductive substrate, and further causinglithium ions to cross from the fourth chamber to the third chamber,through the second lithium ion selective membrane and the secondnon-aqueous electrolyte, and electroplate a second layer of lithium ontothe second face of the conductive substrate, thereby forming the lithiumelectrode, the lithium electrode comprising the conductive substrate,the first layer of lithium, and the second layer of lithium, the firstlayer of lithium having an inner face and an outer face, the inner facebonded to the first face of the conductive substrate, the second layerof having an inner face and an outer face, the inner face bonded to thesecond face of the conductive substrate;

wherein the constant current is between about 10 mA/cm² and about 50mA/cm², and wherein the constant current is applied for a time betweenabout 1 minute and about 60 minutes.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium metal battery is described, comprising:

(1) providing an electrolytic cell, the electrolytic cell including:

-   -   a conductive substrate, stationary within the cell, the        conductive substrate comprising a plate having a first face and        a second face, the first face covered with a first lithium        ion-selective membrane, and the second face covered with a        second lithium ion-selective membrane, the first and second        lithium ion-selective membranes configured to function as solid        state electrolytes;    -   a first chamber containing a first positive electrode, and a        first aqueous lithium salt solution in contact with the first        positive electrode and with the first lithium ion-selective        membrane;    -   a second chamber containing a second positive electrode, and a        second aqueous lithium salt solution in contact with the first        positive electrode and with the second lithium ion-selective        membrane;    -   the electrolytic cell being configured to allow passage of        lithium ions through the first lithium ion selective membrane        between the first chamber and the first face of the conductive        substrate, and to preclude the passage of other chemical species        between the first chamber and the first face of the conductive        substrate;    -   the electrolytic cell being configured to allow passage of        lithium ions through the second lithium ion selective membrane        between the second chamber and the second face of the conductive        substrate, and to preclude the passage of other chemical species        between the second chamber and the second face of the conductive        substrate;

(2) blanketing completely the electrolytic cell with a blanketingatmosphere, the blanketing atmosphere being inert to chemical reactionwith lithium;

(3) applying a variable voltage in order to maintain a constant currentacross the conductive substrate and the first positive electrode, andacross the conductive substrate and the second positive electrode,thereby causing lithium ions to cross from the first chamber through thefirst lithium ion selective membrane, and electroplate a first layer oflithium onto the first face of the conductive substrate, and furthercausing lithium ions to cross from the second chamber through the secondlithium ion selective membrane, and electroplate a second layer oflithium onto the second face of the conductive substrate, therebyforming the lithium electrode, the lithium electrode comprising theconductive substrate, the first layer of lithium, and the second layerof lithium, the first layer of lithium having an inner face and an outerface, the inner face of the first layer of lithium bonded to the firstface of the conductive substrate, and the outer face of the first layerof lithium bonded to the first lithium ion-selective membrane, thesecond layer of lithium having an inner face and an outer face, theinner face of the second layer of lithium bonded to the second face ofthe conductive substrate, and the outer face of the second layer oflithium bonded to the second lithium ion-selective membrane;

wherein the constant current is between about 10 mA/cm² and about 50mA/cm², and wherein the constant current is applied for a time betweenabout 1 minute and about 60 minutes.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium metal electrode is described, wherein a lithiumion selective membrane is immoveable in an electrolytic cell, andwherein as a first layer of lithium is formed, the first layer oflithium displaces non-aqueous electrolyte from a space between theconductive substrate and the lithium ion-selective membrane, therebybonding the inner face of the first layer of lithium to the conductivesubstrate and the outer face of the first layer of lithium to the ionselective membrane, thereby forming a lithium metal electrode comprisingthe conductive substrate and the first layer of lithium metal, with theinner face of the first layer of lithium bonded to the conductivesubstrate, and the outer face of the first layer of lithium bonded tothe lithium ion-selective membrane, which is configured to function as asolid state electrolyte when the lithium metal electrode is incorporatedinto a galvanic cell.

In accordance with an embodiment of the invention, a method ofmanufacturing a lithium metal battery is described, wherein first andsecond lithium ion selective membranes are immovable in an electrolyticcell, and wherein as a first layer of lithium is formed, the first layerof lithium displaces a first non-aqueous electrolyte from a spacebetween a first face of the conductive substrate and the first lithiumion-selective membrane, thereby bonding the inner face of the firstlayer of lithium to the first face of the conductive substrate and theouter face of the first layer of lithium to the first lithium ionselective membrane, and wherein as a second layer of lithium is formed,the second layer of lithium displaces a second non-aqueous electrolytefrom a space between the second face of the conductive substrate and thesecond lithium ion-selective membrane, thereby bonding the inner face ofthe second layer of lithium to the second face of the conductivesubstrate and the outer face of the second layer of lithium to thesecond lithium ion-selective membrane, thereby forming a lithium metalelectrode comprising the conductive substrate and the first and secondlayers of lithium metal, with the inner face of the first layer oflithium bonded to the first face of the conductive substrate, and theouter face of the first layer of lithium bonded to the first lithiumion-selective membrane, and further with the inner face of the secondlayer of lithium bonded to the second face of the conductive substrate,and the outer face of the second layer of lithium bonded to the secondlithium ion-selective membrane, wherein the first and second lithiumion-selective membranes are configured to function as solid stateelectrolytes when the lithium metal electrode is incorporated into agalvanic cell.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing features of embodiments will be more readily understood byreference to the following detailed description, taken with reference tothe accompanying drawings, in which:

FIG. 1 shows steps in manufacturing a lithium metal battery according toan embodiment of the invention.

FIG. 2 shows an improved, single-sided lithium metal electrode, suitablefor use as a working anode of a lithium metal battery, according to anembodiment of the invention.

FIG. 3 shows an electrolytic cell for manufacturing an improved,single-sided lithium metal electrode suitable for use as a working anodein a lithium metal battery, according to an embodiment of the invention.

FIG. 4 shows an improved, double-sided lithium electrode, suitable foruse as a working anode in a lithium metal battery, according to anembodiment of the invention.

FIG. 5 shows an electrolytic cell suitable for manufacturing adouble-sided electrode suitable for use as a working anode in a lithiummetal battery, according to an embodiment of the invention.

FIG. 6 shows a battery having as a working anode a single-sided lithiummetal electrode, with a layer of highly pure lithium metal sandwichedbetween a conductive substrate and a lithium ion selective membrane, thelithium ion selective membrane configured to function as a solid stateelectrolyte.

FIG. 7 shows an electrolytic cell suitable for manufacturing asingle-sided lithium metal electrode as shown in FIG. 6, prior theplating of lithium metal on a conductive substrate of the cell, with aconductive substrate coated with a lithium ion selective membrane.

FIG. 8 shows the electrolytic cell of FIG. 7, after plating of lithiummetal on the conductive substrate, the lithium metal being bonded on oneside to the conductive substrate, and on the opposite side to thesolid-state electrolyte, the electrode being suitable for use as aworking anode in a lithium metal battery, according to an embodiment ofthe invention.

FIG. 9 shows a battery according to an embodiment of the invention, thebattery having as a working anode a double-sided lithium electrode, withlithium metal sandwiched between a conductive substrate and a lithiumion selective membrane, the lithium ion selective membrane configured tofunction as a solid-state electrolyte.

FIG. 10 shows an electrolytic cell suitable for manufacturing adouble-sided lithium metal electrode of the type embodied in FIG. 9,prior to the plating of lithium metal on the two sides of the conductivesubstrate of the cell, wherein the conductive substrate is covered witha lithium ion selective membrane on both of its two faces.

FIG. 11 shows the electrolytic cell of FIG. 10, after plating of lithiummetal on each the two faces of a conductive substrate, where for eachface, the lithium metal is bonded on one side to the conductivesubstrate, and on the opposite side to the solid-state electrolyte, theelectrode being suitable for use as a working anode in a lithium metalbattery, according to an embodiment of the invention.

FIG. 12 shows a lithium ion battery manufacturing facility, according toPrior Art.

FIG. 13 shows a vertically integrated lithium metal batterymanufacturing facility with manufacturing as embodied in the methodsdescribed in the current application.

FIG. 14 shows a battery case for a battery with a single-sided lithiumanode according to embodiments of the invention.

FIG. 15 shows a battery case for a battery with a double-sided lithiumanode according to embodiments of the invention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

Definitions. As used in this description and the accompanying claims,the following terms shall have the meanings indicated, unless thecontext otherwise requires:

A “cathode” is an electrode where reduction occurs.

An “anode” is an electrode where oxidation occurs.

A “working anode” is the anode in a galvanic cell.

A “positive electrode” is the anode in an electrolytic cell, and thecathode in a galvanic cell.

A “negative electrode” is the cathode in an electrolytic cell and theanode in a galvanic cell. Consequently, a lithium metal electrode isalways a “negative electrode” even though it is a cathode in anelectrolytic cell and an anode in a galvanic cell.

In the context of this application, a “lithium metal electrode” and a“lithium electrode” are synonymous, and each refers to a negativeelectrode comprising lithium metal.

A “lithium metal battery” (or “LMB”) is a battery that utilizes anegative electrode comprising pure lithium metal (i.e. a lithium metalelectrode). The positive electrode for such a battery is typically anintercalation compound such as Ti₂S, which, during discharge, acceptselectrons through an external circuit from the anode, and intercalatesLi⁺ into its lattice structure.

A “lithium ion battery” is a rechargeable battery where lithium ionsshuttle between a negative electrode and an intercalation compound asthe positive electrode.

A blanketing atmosphere is “substantially free” of lithium reactivecomponents when the atmosphere includes no more than 10 ppm of lithiumreactive components.

In the context of this disclosure, a “vertically integrated” lithiummetal manufacturing facility is a facility where lithium metal anodesare fabricated by electrodepositing at the facility, and integrated intothe battery manufacturing process.

FIG. 1 shows steps in manufacturing a lithium metal battery (LMB)according to embodiments of the current invention. An electrolytic cell,such as in the embodiments of FIGS. 2, 4, 6, 7, 9, and 10 is blanketedwith blanketing atmosphere 2, the blanketing atmosphere beingsubstantially free of lithium reactive components, including nitrogen,oxygen, ozone, oxides of nitrogen, sulfur and phosphorous, carbondioxide, halogens, hydrogen halides, and water. In some embodiments, theblanketing atmosphere includes no more than 10 ppm of lithium reactivecomponents on a molar basis. In some embodiments, the blanketingatmosphere includes no more than 5 ppm of lithium reactive components ona molar basis. In preferred embodiments, the blanketing atmospherecontains no more than 10 ppm nitrogen on a molar basis. In preferredembodiments, the blanketing atmosphere contains no more than 5 ppmnitrogen on a molar basis. In preferred embodiments, the blanketingatmosphere contains no more than 1 ppm nitrogen on a molar basis. Inpreferred embodiments, the blanketing atmosphere is argon gas. Inpreferred embodiments, the argon gas has a purity of greater than 99.998weight percent. The electrolytic cell operates at or near roomtemperature, and uses an aqueous lithium salt solution as an anolyteproviding a lithium feed for electrodepositing to form a negativeelectrode. In preferred embodiments, the aqueous lithium salt solutionincludes lithium sulfate (Li₂SO₄) and/or lithium carbonate (Li₂CO₃).When a Li₂SO₄ solution is used as feed, the only byproduct is O₂ gaswhich is generated at the anode, vented from the anolyte, and does notcome into contact with the inert catholyte area. Li₂SO₄ is a lithiumfeedstock that is very low in the process chain, and thus Li₂SO₄solutions provide an economical source of lithium ions for methodsaccording to the instant invention. When Li₂CO₃ is used as feedstock,the minimal amount of carbon dioxide generated can likewise be ventedoff at the anode of the electrolysis cell. Typically, Li₂CO₃ is moreexpensive than Li₂SO₄. However, it is not uncommon for batterymanufacturers to receive lithium carbonate that fails to meet qualitycontrol standards, and such lithium carbonate could be easily repurposedfor lithium metal production. The aqueous lithium salt solutions do notneed to be highly concentrated since as lithium ions are depleted byelectrodeposition, flow cells may allow depleted lithium ions to bereplaced.

Voltage across the electrolytic cell is regulated in order to apply aconstant current to the cell 4. The applied voltage causes lithium ionsto flow across a lithium ion-selective membrane from the anolyte to acatholyte 6, wherein the lithium ion-selective membrane is configured toallow the passage of lithium ion but to preclude the passage of otherchemical species. At the cathode, lithium ion is reduced to the lithiummetal, thereby plating onto a conductive substrate, and forming alithium metal electrode 8. In some embodiments the conductive substrateis selected from the group consisting of copper, aluminum, graphitecoated copper, and nickel. In a preferred embodiment, the conductivesubstrate is copper. When constant current is applied within the rangeof about 10 mA/cm² to about 50 mA/cm², the lithium ions crossing thelithium ion selective membrane and electrodepositing onto a conductivesubstrate do not produce nanorods or dendrites. Rather, current withinthis range produces an extremely dense lithium metal deposit and allowselectrodeposition to proceed to completion in between one and 60minutes. In preferred embodiments, the constant current applied is about10 mA/cm² to about 50 mA/cm². In preferred embodiments, the constantcurrent applied is about 25 mA/cm² to about 50 mA/cm². In preferredembodiments, the constant current applied is about 40 mA/cm² to about 50mA/cm². In preferred embodiments, the density of the lithium metaldeposited ranges from about 0.4 g/cm³ to 0.543 g/cm³. In some preferredembodiments the density of lithium metal deposited ranges from 0.45g/cm³ to 0.543 g/cm³. A constant current of about 10 mA/cm² to about 50mA/cm² is higher than the operating current during charge/dischargecycles of operating batteries manufactured using lithium metalelectrodes of the invention. Lithium metal electrodes formed at highercurrent densities than are used in an operating battery enhance thecharge-discharge recycling capacity of such batteries. Without beingbound by theory, it is believed that lithium metal electrodes formed athigher current densities than are used in an operating battery will notform dendrites upon cycling if there are no impurities elsewhere in thebattery. During the electrodeposition process, lithium continuallypasses through a lithium ion selective membrane and accumulates on theconductive substrate until the desired thickness is achieved (a film of15 μm can be made in under five minutes). Only lithium ions pass throughfrom the lithium ion containing aqueous electrolyte, allowing for theuse of inexpensive impure feed solutions containing Li₂SO₄. and/orLi₂CO₃. The lithium electrodeposited on the negative electrode iselementally pure and remains so because it is never handled or exposedto air prior to entering a battery. Because the electrodepositing occursin a blanketing atmosphere substantially free of lithium-reactivecomponents, including nitrogen, the formation of impurities, includingin particular Li₃N, is avoided.

In some embodiments, the lithium electrodeposited on the negativeelectrode coats all sides of the negative electrode. In someembodiments, the copper is in the form of a mesh. In some embodiments,the copper is in the form of a foam. In some embodiments, the conductivesubstrate comprises a plate with two faces, and lithium metal coats atleast one face of the plate. In some embodiments, the lithium metalcoats both of the two faces of the plate.

In some embodiments, the lithium ion selective membrane is a hybridorganic-inorganic membrane including a polymeric matrix and a pluralityof ion-conducting particles disposed within the polymeric matrix. Insome such embodiments, an inorganic coating is deposited on thepolymeric matrix, the inorganic coating being a uniform layer of 1 to10,000 atoms thick. In some embodiments, the polymer may be asilica-based polyurethane, polyethylene oxide, polystyrene, or apolyamide.

In some embodiments, the lithium ion selective membrane comprises aglass frit with lithium ion conducting particles disposed within.

In some embodiments, the ion conducting particles are selected from thegroup consisting of LiFePO₄, LiCoO₂, NASICON electrolytes,lithium-lanthanum titanates (LLTO), garnet type electrolytes, LISICONand Thio-LISICON electrolytes, Li₇La3Zr3O₁₂ (LLZO), the cubic phase(c-LLZO).

Finally, the lithium metal electrode thus formed is used in thefabrication of a LMB 12. In a preferred embodiment, all of the steps inthe manufacturing method are performed at a single manufacturingfacility. In some embodiments, the single manufacturing facility iscontained in an area of no greater than 10 km². In some embodiments themanufacturing facility is contained in an area less than about 1 km².Because lithium metal batteries of the instant invention are fabricatedin a fully charged state, the invention reduces the footprint, cost andtime of rechargeable batteries compared to conventional LIBs, which areinitially fabricated in an uncharged state, and require time-consumingfinishing steps to obtain a fully charged battery.

FIG. 2 provides a single-sided lithium electrode 15 according to anembodiment of the invention. The lithium electrode 15 includes aconductive substrate 10, in the form of a plate having two faces. Inpreferred embodiments, the conductive substrate is selected from thegroup consisting of copper, aluminum, graphite coated copper, andnickel. Bonded to one of the two faces of the conductive substrate is alayer of lithium metal 60, the lithium metal including no more than 5ppm of non-metallic elements by mass. In a preferred embodiment, thelithium metal includes no more than 1 ppm of non-metallic elements bymass. In a preferred embodiment, the lithium metal includes no more than1 ppm of nitrogen by mass. In a preferred embodiment, the layer oflithium metal 60 has a thickness between about 1 micron and about 10microns. The conductive substrate 10 and the layer of lithium metal 60together comprise the single-sided lithium metal electrode 15, suitablefor use as a fully charged working anode in a LMB. In a preferredembodiment, the lithium metal electrode 15 has a specific capacity ofgreater than about 3800 mAh per gram of lithium metal. In a preferredembodiment, the layer of lithium metal 60 has a density of between about0.4 g/cm³ and about 0.534 g/cm³. In a preferred embodiment, the layer oflithium metal 60 has a density of between about 0.45 g/cm³ and about0.543 g/cm³.

In a method of manufacturing the single-sided lithium electrode 15 shownin FIG. 2, an electrolytic cell 5 is used, as shown in FIG. 3. Duringthe manufacturing process, the electrolytic cell 5 of this embodiment iscompletely blanketed with a blanketing atmosphere 24, the blanketingatmosphere being substantially free of lithium reactive components. In apreferred embodiment, the blanketing atmosphere includes no more than 10ppm of lithium reactive components on a molar basis. In a preferredembodiment, the blanketing atmosphere includes no more than 5 ppm oflithium reactive components on a molar basis. In a preferred embodiment,the blanketing atmosphere includes no more than 10 ppm of nitrogen on aper molar basis. In a preferred embodiment, the blanketing atmosphereincludes no more than 5 ppm of nitrogen on a per molar basis. In apreferred embodiment, the blanketing atmosphere includes no more than 1ppm of nitrogen on a per molar basis. In a preferred environment, theblanketing atmosphere comprises argon with a purity of greater than99.998 weight percent. In the embodiment of FIG. 3, the blanketingatmosphere 24 and the electrolytic cell 5 are enclosed in agas-impermeable container 500. The cell 5 includes a first chamber 26and a second chamber 28. The first chamber 26 contains a positiveelectrode 20 and an aqueous lithium salt solution 40 in contact with thepositive electrode 20. The second chamber 28 contains the lithium metalelectrode 15, a lithium ion-selective membrane 50, and a non-aqueouselectrolyte 30. The lithium ion selective membrane 50 has a first sideand a second side, and physically separates the first chamber 26 fromthe second chamber 28, contacting the aqueous lithium salt solution 40on the first side. In the second chamber 28, the non-aqueous electrolyte30 is disposed between the lithium metal electrode 15 and the secondside of the lithium ion-selective membrane 50, physically contactingboth the lithium metal electrode 15 and the second side of the lithiumion-selective membrane 50. The lithium metal electrode 15 includes aconductive substrate 10, stationary during lithium metalelectrodeposition within the second chamber, electrodeposited with alayer of elemental lithium 60. The lithium ion selective membrane 50allows lithium ions to pass between the first chamber 26 and the secondchamber 28, but precludes the passage of other chemical species betweenthe two chambers. In particular, the lithium ion selective membrane doesnot allow water to pass from the first chamber 26 to the second chamber28.

In manufacturing the single-sided lithium metal electrode 15 embodied inFIG. 2, a variable voltage is applied across the positive electrode 20and the conductive substrate 10 of the electrolytic cell 5, in order tomaintain a constant current, thereby causing lithium ions to movethrough the aqueous lithium salt solution 40, cross from the firstchamber 26 to the second chamber 28, through the lithium ion selectivemembrane 50, into the non-aqueous electrolyte, travel to the surface ofthe stationary conductive substrate 10, where each lithium ion gains anelectron, thereby causing the layer of elemental lithium 60 to beelectrodeposited on the conductive substrate 10, thereby forming thesingle-sided lithium metal electrode 15.

In some embodiments, the first chamber 26 of the electrolytic cell 5 ofFIG. 2 is a flow chamber, with an entrance port 70 and an exit port 80allowing aqueous lithium salt solution to enter the first chamber 26 toprovide a renewable supply of lithium ions for electrodepositing.

In preferred embodiments, the constant current is between about 10mA/cm² and about 50 mA/cm². In preferred embodiments, the constantcurrent applied is about 25 mA/cm² to about 50 mA/cm². In preferredembodiments, the constant current applied is about 40 mA/cm² to about 50mA/cm². In preferred embodiments, the constant current is applied for atime between about 1 minute and about 60 minutes.

In preferred embodiments, the aqueous lithium salt solution 40 isselected from the group consisting of Li₂SO₄, Li₂CO₃, and combinationsthereof. In preferred embodiments, the aqueous lithium salt solution 40includes Li₂SO₄. In preferred embodiments, the lithium ion selectivemembrane 50 comprises a polymeric matrix and a plurality ofion-conducting particles disposed within the polymeric matrix. In apreferred embodiment, the lithium ion selective membrane 50 includes aglass frit with lithium ion conducting particles disposed within.

FIG. 4 provides a double-sided lithium metal electrode, according to anembodiment of the invention. The double-sided lithium metal electrode115 includes a conductive substrate 110, in the form of a plate having afirst face and a second face. In preferred embodiments, the conductivesubstrate 115 is selected from the group consisting of copper, aluminum,graphite coated copper, and nickel. The first face and a second face ofthe conductive substrate 115 are coated with a layer of lithium metal,160 a and 160 b, respectively, the lithium metal including no more than5 ppm of non-metallic elements by mass. In a preferred embodiment, thelithium metal includes no more than 1 ppm of non-metallic elements bymass. In a preferred embodiment, the layer of lithium metal 160 a, 160 bhas a thickness between about 1 micron and about 10 microns. Theconductive substrate 110 and the layers of lithium metal 160 a and 160 btogether comprise the double-sided lithium metal electrode 115, which issuitable for use as a fully charged working anode in a LMB. In apreferred embodiment, the lithium metal electrode 115 has a specificcapacity of greater than about 3800 mAh per gram of lithium metal. In apreferred embodiment, the layers of lithium metal 160 a, 160 b each havea density of between about 0.4 g/cm³ and about 0.543 g/cm³. In apreferred embodiment, the layers of lithium metal 160 a, 160 b each havea density of between about 0.45 g/cm³ and about 0.543 g/cm³.

In a method of manufacturing the double-sided lithium electrode 115shown in FIG. 4, an electrolytic cell 105 is used, as shown in FIG. 5.During the manufacturing process, the electrolytic cell 105 of thisembodiment is blanketed with a blanketing atmosphere 24, the blanketingatmosphere 24 being inert to chemical reaction with lithium. In apreferred embodiment, the blanketing atmosphere includes no more than 10ppm of lithium reactive components on a molar basis. In a preferredembodiment, the blanketing atmosphere includes no more than 5 ppm oflithium reactive components on a molar basis. In a preferred embodiment,the blanketing atmosphere includes no more than 10 ppm of nitrogen on aper molar basis. In a preferred embodiment, the blanketing atmosphereincludes no more than 5 ppm of nitrogen on a per molar basis. In apreferred embodiment, the blanketing atmosphere includes no more than 1ppm of nitrogen on a per molar basis. In a preferred environment, theblanketing atmosphere comprises argon with a purity of greater than99.998 weight percent. In the embodiment of FIG. 5, the blanketingatmosphere 24 and the electrolytic cell 105 are enclosed in agas-impermeable container 500. The cell 105 includes a first chamber 126a, a second chamber 128 a, a third chamber 126 b, and a fourth chamber128 b. The first chamber 126 a contains a positive electrode 120 a andan aqueous lithium salt solution 140 a in contact with the positiveelectrode 120 a and the third chamber 126 b contains a positiveelectrode 120 b and an aqueous lithium salt solution 140 b in contactwith the positive electrode 120 b. The second chamber 128 a and thefourth chamber 128 b share the double-sided lithium metal electrode 115,which bounds the two chambers, the double-sided lithium metal electrode115 including a central conductive substrate 110 having a first face anda second face, the first and the second faces electrodeposited with thelayers of lithium metal 160 a, 160 b, respectively, with the layer oflithium metal 160 a extending into the second chamber 128 a, and thelayer of lithium metal 160 b extending into the fourth chamber. Thesecond chamber 128 a contains a lithium ion-selective membrane 150 a,and a non-aqueous electrolyte 130 a. The lithium ion selective membrane150 a has a first side and a second side, and physically separates thefirst chamber 126 a from the second chamber 128 a, contacting theaqueous lithium salt solution 140 a on the first side. In the secondchamber 128 a, the non-aqueous electrolyte 130 a is disposed between thelithium metal layer 160 a and the second side of the lithiumion-selective membrane 150 a. The fourth chamber contains a lithiumion-selective membrane 150 b, and a non-aqueous electrolyte 130 b. Thelithium ion selective membrane 150 b has a first side and a second side,and physically separates the third chamber 126 b from the fourth chamber128 b, contacting the aqueous lithium salt solution 140 b on the firstside. In the fourth chamber 128 b, the non-aqueous electrolyte 130 b isdisposed between the lithium metal layer 160 b and the second side ofthe lithium ion-selective membrane 150 b. The lithium ion selectivemembranes 150 a, 150 b allow lithium ions to pass between first chamber126 a and the second chamber 128 a, and between the third chamber 126 band the fourth chamber 128 b, respectively, but preclude the passage ofother chemical species between the first and second chambers 126 a, 128a and between the third and the fourth chambers 126 b, 128 b,respectively.

In manufacturing the double-sided lithium metal electrode 115 embodiedin FIG. 4 using the electrolytic cell 105, a variable voltage is appliedacross the positive electrodes 120 a, 120 b and the conductive substrate110 of the electrolytic cell 105, in order to maintain a constantcurrent, thereby causing lithium ions to move through the aqueouslithium salt solutions 140 a, 140 b, cross from the first and thirdchambers 126 a, 126 b to the second and fourth chambers 128 a, 128 b,respectively, through the respective lithium ion selective membranes 150a, 150 b, and into the non-aqueous electrolytes 130 a, 130 b,respectively, travel to the first and second faces of the conductivesubstrate 110, where each lithium ion gains an electron, thereby causinglayers of elemental lithium 160 a, 160 b to be electrodeposited,respectively, on the first face and the second face of the conductivesubstrate 110, thereby forming the double-sided lithium metal electrode115. During electrodeposition of the lithium metal layers 160 a, 160 bonto the first face and the second face of the conductive substrate 110,the conductive substrate 110 remains stationary.

In some embodiments, the first and third chambers 126 a, 126 b of theelectrolytic cell 105 of FIG. 4 are flow chambers, with entrance ports170 a, 170 b and exit ports 180 a, 180 b allowing aqueous lithium saltsolutions 140 a, 140 b to enter the first chamber 126 a and the thirdchamber 126 b to provide a renewable supply of lithium ions forelectrodepositing.

In preferred embodiments, the constant current is between about 10mA/cm² and about 50 mA/cm². In preferred embodiments, the constantcurrent applied is about 25 mA/cm² to about 50 mA/cm². In preferredembodiments, the constant current applied is about 40 mA/cm² to about 50mA/cm². In preferred embodiments, the constant current is applied for atime between about 1 minute and about 60 minutes.

In preferred embodiments, the aqueous lithium salt solution 140 a, 140 bis selected from the group consisting of Li₂SO₄, Li₂CO₃, andcombinations thereof. In preferred embodiments, the aqueous lithium saltsolution 140 a, 140 b includes Li₂SO₄. In preferred embodiments, thelithium ion selective membrane 150 a, 150 b comprises a polymeric matrixand a plurality of ion-conducting particles disposed within thepolymeric matrix. In a preferred embodiment, the lithium ion selectivemembrane 150 a, 150 b includes a glass frit with lithium ion conductingparticles disposed within.

FIG. 6 provides a galvanic cell 225 manufactured with a single-sidedlithium metal electrode 215 configured to function as an anode. Thelithium metal electrode 215 includes a conductive substrate 210, bondedto a layer of lithium metal 260, the lithium metal including no morethan 5 ppm of non-metallic elements by mass. In a preferred embodiment,the lithium metal includes no more than 1 ppm of non-metallic elementsby mass. In a preferred embodiment, the lithium metal includes no morethan 1 ppm of nitrogen by mass. The conductive substrate 210 and thelayer of lithium metal 260 together comprise the single-sided lithiummetal electrode 215, of the galvanic cell 225. In a preferredembodiment, the lithium metal electrode 215 has a specific capacity ofgreater than about 3800 mAh per gram of lithium metal. In a preferredembodiment, the layer of lithium metal 60 has a density of between about0.4 g/cm³ and about 0.534 g/cm³. In a preferred embodiment, the layer oflithium metal 260 has a density of between about 0.45 g/cm³ and about0.543 g/cm³. In preferred embodiments, the conductive substrate isselected from the group consisting of copper, aluminum, graphite coatedcopper, and nickel. The layer of lithium metal 260 has a first face anda second face and is bonded on the first face to the conductivesubstrate 210 and on the second face to the lithium ion-selectivemembrane 250. The lithium ion-selective membrane 250, is configured tofunction as a solid state electrolyte. The lithium ion-selectivemembrane 250 separates the layer of lithium metal 260 from a catholyte290. In preferred embodiments, the catholyte 290 includes ionicliquid-forming salts. In preferred embodiments, the catholyte 290comprises an ionic liquid. The catholyte 290 in turn separates thelithium ion-selective membrane 250 from a cathode/catholyte interface295, which covers a face of a cathode 235, separating the cathode 235from the catholyte 290. Electrical contacts to the anode 245 allowelectrons to flow from the electrode 215 to corresponding electricalcontacts to the cathode 255, and then on to the cathode 235. In thisconfiguration, the lithium ion-selective membrane 250 is configured tofunction as a solid state electrolyte. During discharge of the battery,the layer of pure lithium metal is oxidized to lithium ions, releasingelectrons which flow through the electrical contacts 245, 255 from thesingle-sided electrode 215 to the cathode 235, and lithium ions, whichflow through the lithium ion-selective membrane 250 into the catholyte290, and into the cathode 235, where electrons are taken up. In variousembodiments, the catholyte 290 can include an organic cation and aninorganic ion, comprising a salt capable of forming an ionic liquid. Inembodiments, the catholyte 290 comprises an ionic liquid. Inembodiments, the catholyte 290 comprises lithium salts of an organicanion capable of forming ionic liquids, the organic anions selected fromthe group consisting of trifluoromethanesulfonyl-imide (TFSI),N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide(Pyr₁₄TFSI), trifluoromethanesulfonyl-imide,bis(trifluoromethanesulfonyl)imide (LiTFSI), and1-ethyl-₃-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI). In some embodiments, the catholyte 290 comprises ionicliquid-forming salts dissolved in 1,3-dioxolane (DOL), 1,2dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME).In an embodiment, the catholyte comprises concentrated (4.0-5.0 M)lithium bis(fluorosulfonyl) imide (LiFSI) in 1:1 DOL/DME.

Without being bound by theory, it is believed that elementally purelithium metal chemically bonded to a substrate which is then chemicallybonded to a lithium ion selective membrane configured to function as asolid state electrolyte will eliminate impedance variations at theelectrode/solid electrolyte separator interface, thereby minimizingdendrite formation.

In a method of manufacturing by electrodeposition the single-sidedlithium electrode 215 of the galvanic cell 225 of FIG. 6, anelectrolytic cell 205 is used. FIG. 7 shows the electrolytic cell 205prior to electrodeposition and FIG. 8 shows the electrolytic cellfollowing electrodeposition. According to the method, the electrolyticcell 205 is completely blanketed with a blanketing atmosphere 24, theblanketing atmosphere being inert to chemical reaction with lithium. Ina preferred embodiment, the blanketing atmosphere includes no more than10 ppm of lithium reactive components on a molar basis. In a preferredembodiment, the blanketing atmosphere includes no more than 5 ppm oflithium reactive components on a molar basis. In a preferred embodiment,the blanketing atmosphere includes no more than 10 ppm of nitrogen on aper molar basis. In a preferred embodiment, the blanketing atmosphereincludes no more than 5 ppm of nitrogen on a per molar basis. In apreferred embodiment, the blanketing atmosphere includes no more than 1ppm of nitrogen on a per molar basis. In a preferred environment, theblanketing atmosphere comprises argon with a purity of greater than99.998 weight percent. In the embodiment of FIGS. 7 and 8, theblanketing atmosphere 24 and the electrolytic cell 5 are enclosed in agas-impermeable container 500. During the process of electrodeposition,the electrolytic cell 205 is confined to the blanketing atmosphere 24.

The electrolytic cell 205 includes a conductive substrate 210,configured as a negative electrode, an ion-selective membrane 250, anaqueous lithium salt solution 240, and a positive electrode 220. Theaqueous lithium salt solution 240 is interposed between the conductivesubstrate 210 and the positive electrode 220. Prior toelectrodeposition, as shown in FIG. 7, the lithium ion selectivemembrane 250 covers the conductive substrate 210, and forms a barrierseparating the lithium salt solution 240 and the conductive substrate210. Prior to electrodeposition, as shown in FIG. 7, the conductivesubstrate 210 is physically coated with a lithium ion-selective membrane250, configured to function as a solid state electrolyte. Afterelectrodeposition, as shown in FIG. 8, a layer of lithium metal 260 iselectrodeposited between the conductive substrate 210 and the lithiumion selective membrane 250, bonding to both the conductive substrate 210and to the lithium ion selective membrane 250. During the process ofelectrodeposition, the lithium ion-selective membrane 250 separates theconductive substrate 210 and the electrodeposited lithium metal layer260 from the lithium salt solution 240. The lithium ion selectivemembrane 250 is configured to function as a solid state electrolyte,allowing the passage of lithium ions from the aqueous salt solution 240to electrodeposit onto the surface of the conductive substrate 210, butprecluding the passage of other chemical species.

In manufacturing the single-sided lithium metal electrode 215 for thegalvanic cell embodied in FIG. 6, a variable voltage is applied acrossthe positive electrode 220 and the conductive substrate 210 of theelectrolytic cell 205, in order to maintain a constant current, therebycausing lithium ions to move through the aqueous lithium salt solution240, through the lithium ion-selective membrane 250, travel to thesurface of the conductive substrate 210, where each lithium ion gains anelectron, thereby electrodepositing a layer of elemental lithium 260onto the conductive substrate 210, the layer of elemental lithium thusforming and bonding to the conductive substrate on a first side of thelayer of elemental lithium 260 and the lithium ion-selective membrane250 on a second side of the layer of elemental lithium 260. In thismanner, as shown in FIGS. 7 and 8, the single-sided lithium metalelectrode 215 is manufactured so that a sandwich of the layer of lithiummetal 260 is formed between the conductive substrate 210 and the lithiumion-selective membrane 250. During the process of electrodeposition, theconductive substrate 210 is stationary in the electrolytic cell.

In some embodiments, the electrolytic cell 205 of FIG. 7 is a flowchamber, with an entrance port 270 and an exit port 280 allowing aqueouslithium salt solution 240 to enter the electrolytic cell 205 to providea renewable supply of lithium ions for electrodepositing.

In preferred embodiments, the constant current is between about 10mA/cm² and about 50 mA/cm². In preferred embodiments, the constantcurrent applied is about 25 mA/cm² to about 50 mA/cm². In preferredembodiments, the constant current applied is about 40 mA/cm² to about 50mA/cm². In preferred embodiments, the constant current is applied for atime between about 1 minute and about 60 minutes.

In preferred embodiments, the aqueous lithium salt solution 240 isselected from the group consisting of Li₂SO₄, Li₂CO₃, and combinationsthereof. In preferred embodiments, the aqueous lithium salt solution 240includes Li₂SO₄. In preferred embodiments, the lithium ion selectivemembrane 250 comprises a polymeric matrix and a plurality ofion-conducting particles disposed within the polymeric matrix. In apreferred embodiment, the lithium ion selective membrane 250 includes aglass frit with lithium ion conducting particles disposed within.

In an alternative method of manufacturing by electrodeposition thesingle-sided lithium electrode 215 of the galvanic cell 225 of FIG. 6,the electrolytic cell 5 of FIG. 3 is used. According to this method, thelithium ion selective membrane 50 and the conductive substrate 10 bothremain stationary in the electrolytic cell. A variable voltage isapplied across the positive electrode 20 and the conductive substrate 10of the electrolytic cell 5, in order to maintain a constant current,thereby causing lithium ions to move through the aqueous lithium saltsolution 40, cross from the first chamber 26 to the second chamber 28,through the lithium ion selective membrane 50, into the non-aqueouselectrolyte, travel to the surface of the conductive substrate 10, whereeach lithium ion gains an electron, thereby causing the layer ofelemental lithium 60 to be electrodeposited on the conductive substrate10. As the layer of elemental lithium 60 grows, it displaces non-aqueouselectrolyte 30 from the second chamber 28, eventually coming intocontact with and bonding to the lithium ion selective membrane 50,thereby forming the single-sided lithium metal electrode 215 of FIG. 6,comprising the conductive substrate 10 and the layer of lithium 60,wherein the layer of lithium 60 is bonded on one face to the conductivesubstrate 10 and on the other face to the lithium ion-selective membrane50, which is configured to function as a solid state electrolyte.

FIG. 9 provides a galvanic cell 325 manufactured with a double-sidedlithium metal electrode 315, configured to function as an anode. Thedouble-sided lithium metal electrode 315 includes a conductive substrate310, in the form of a plate having a first face and a second face, withthe first face and the second face bonded to first and second lithiummetal sheets, 360 a and 360 b, respectively, the lithium metal includingno more than 5 ppm of non-metallic elements by mass. In a preferredembodiment, the lithium metal includes no more than 1 ppm ofnon-metallic elements by mass. In a preferred embodiment, the lithiummetal includes no more than 1 ppm of nitrogen by mass. The conductivesubstrate 310 and the first and second layers of lithium metal, 360 a,360 b, respectively, together comprise the double-sided lithium metalelectrode 315 of the galvanic cell 325. In a preferred embodiment, thelithium metal electrode 315 has a specific capacity of greater thanabout 3800 mAh per gram of lithium metal. In a preferred embodiment, thefirst and the second layers of lithium metal 360 a, 360 b, each has adensity of between about 0.4 g/cm³ and about 0.534 g/cm³. In a preferredembodiment, the layers of lithium metal 360 a, 360 b, each has a densityof between about 0.45 g/cm³ and about 0.543 g/cm³. In preferredembodiments, the conductive substrate is selected from the groupconsisting of copper, aluminum, graphite coated copper, and nickel. Eachlayer of lithium metal 360 a, 360 b has a first face and a second faceand is bonded on the first face to the conductive substrate 310 and onthe second face to the lithium ion-selective membrane 350 a, 350 b,respectively. The lithium ion-selective membranes 350 a, 350 b, areconfigured to function as solid state electrolytes. The lithiumion-selective membrane 350 a separates the layer of lithium metal 360 afrom a catholyte 390 a. In preferred embodiments, the catholyte 390 aincludes ionic liquid-forming salts. In preferred embodiments, thecatholyte 390 a comprises an ionic liquid. The catholyte 390 a in turnseparates the lithium ion-selective membrane 350 a from acathode/catholyte interface 395 a, which covers a face of a cathode 335a, separating the cathode 335 a from the ionic liquid 390 a. The lithiumion-selective membrane 350 b separates the layer of lithium metal 360 bfrom a catholyte 390 b. In preferred embodiments, the catholyte 390 bincludes ionic liquid-forming salts. In preferred embodiments, thecatholyte 390 b comprises an ionic liquid. The catholyte 390 b in turnseparates the lithium ion-selective membrane 350 b from acathode/catholyte interface 395 b, which covers a face of a cathode 335b, separating the cathode 335 b from the ionic liquid 390 b.

An electrical contact to the anode 345 allows electrons to flow from theelectrode 315 to corresponding electrical contacts to the two cathodes355 a, 355 b and then on to the cathodes 335 a, 335 b, respectively.During discharge of the battery, the layers of pure lithium metal 360 a,360 b are oxidized to lithium ions, releasing electrons which flowthrough the electrical contact 345, through the electrical contacts 355a, 355 b from the double-sided electrode 315 to the cathodes 335 a, 335b and lithium ions, which flow through the lithium ion-selectivemembranes 350 a, 350 b into the ionic liquids 390 a, 390 b, and into thecathodes, 335 a, 335 b, where they intercalate into the cathodes 335 a,335 b where electrons are taken up. In various embodiments, thecatholyte can include an organic cation and an inorganic ion, comprisinga salt capable of forming an ionic liquid. In various embodiments, thecatholytes 390 a, 390 b can include an organic cation and an inorganicion, comprising a salt capable of forming an ionic liquid. Inembodiments, the catholytes 390 a, 390 b comprise an ionic liquid. Inembodiments, the catholytes 390 a, 390 b comprise lithium salts of anorganic anion capable of forming ionic liquids, the organic anionsselected from the group consisting of trifluoromethanesulfonyl-imide(TFSI), N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide(Pyr₁₄TFSI), trifluoromethanesulfonyl-imide,bis(trifluoromethanesulfonyl)imide (LiTF SI), and1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI). In some embodiments, the catholytes 390 a, 390 b comprise ionicliquid-forming salts dissolved in 1,3-dioxolane (DOL), 1,2dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME).In an embodiment, the catholytes 390 a, 390 b comprise concentrated(4.0-5.0 M) lithium bis(fluorosulfonyl) imide (LiFSI) in 1:1 DOL/DME.

Without being bound by theory, it is believed that elementally purelithium metal chemically bonded to a substrate which is then chemicallybonded to a lithium ion selective membrane configured to function as asolid state electrolyte will eliminate impedance variations at theelectrode/solid electrolyte separator interface, thereby minimizingdendrite formation.

In a method of manufacturing by electrodeposition the double-sidedlithium electrode 315 of the galvanic cell 325 of FIG. 9, anelectrolytic cell 305 is used. FIG. 10 shows the electrolytic cell 305prior to electrodeposition and FIG. 11 shows the electrolytic cellfollowing electrodeposition. According to the method, the electrolyticcell 305 is completely blanketed with a blanketing atmosphere 24, theblanketing atmosphere being inert to chemical reaction with lithium. Ina preferred embodiment, the blanketing atmosphere includes no more than10 ppm of lithium reactive components on a molar basis. In a preferredembodiment, the blanketing atmosphere includes no more than 5 ppm oflithium reactive components on a molar basis. In a preferred embodiment,the blanketing atmosphere includes no more than 10 ppm of nitrogen on aper molar basis. In a preferred embodiment, the blanketing atmosphereincludes no more than 5 ppm of nitrogen on a per molar basis. . In apreferred embodiment, the blanketing atmosphere includes no more than 1ppm of nitrogen on a per molar basis. In a preferred environment, theblanketing atmosphere comprises argon with a purity of greater than99.998 weight percent. In the embodiment of FIGS. 11 and 12, theblanketing atmosphere 24 and the electrolytic cell 5 are enclosed in agas-impermeable container 500. During the process of electrodeposition,the electrolytic cell 305 is confined to the blanketing atmosphere 24.

The electrolytic cell 305 includes a first chamber 326 a, and a secondchamber 326 b, the first chamber having a proximal end and a distal end,and the second chamber having a proximal and a distal end. Contiguous toand separating the first chamber 326 a from the second chamber 326 b isthe conductive substrate 310, the conductive substrate 310 having afirst side facing the first chamber 326 a and a second side facing thesecond chamber 326 b. Prior to electrodeposition, as embodied in FIG.10, the first side and the second side of the conductive substrate 310are coated with, respectively, a first lithium ion-selective membrane350 a configured to function as a solid state electrolyte, extendinginto the proximal end of the first chamber 326 a, and a second lithiumion-selective membrane 350 b, configured to function as a solid stateelectrolyte, extending into the proximal end of the second chamber 326b. At their distal ends, the first chamber 326 a and the secondchambers, 326 b contain, respectively, positive electrodes 320 a and 320b. The positive electrode 320 a and the first lithium ion-selectivemembrane 350 a are separated by an aqueous salt solution 340 a, theaqueous salt solution 340 a physically contacting both the positiveelectrode 320 a and the lithium ion-selective membrane 350 a. In a likemanner, the positive electrode 320 b and the first lithium ion-selectivemembrane 350 b are separated by an aqueous salt solution 340 b, theaqueous salt solution 340 b physically contacting both the positiveelectrode 320 b and the lithium ion-selective membrane 350 b.

After electrodeposition, as shown in FIG. 11, layers of lithium metal,320 a, 320 b, are electrodeposited between the conductive substrate 310and the lithium ion selective membranes, 350 a, 350 b, respectively, thelayers of lithium metal 320 a, 320 b, bonding to the conductivesubstrate 310 and the lithium ion selective membranes 350 a, 350 b,respectively.

During the process of electrodeposition, the lithium ion-selectivemembranes 350 a, 350 b, separate the conductive substrate 310 and theelectrodeposited lithium metal layers 360 a, 360 b, respectively, fromthe lithium salt solutions 340 a, 340 b.

The lithium ion-selective membranes 350 a, 350 b are configured functionas solid state electrolytes, allowing lithium ions to pass between theaqueous lithium salt solutions 340 a, 340 b, and the conductivesubstrate 310, but preventing the passage of other chemical species.

In manufacturing the double-sided lithium metal electrode 315 for thegalvanic cell embodied in FIG. 9, a variable voltage is applied acrossthe positive electrodes 320 a, 320 b and the conductive substrate 310 ofthe electrolytic cell 305, in order to maintain a constant current,thereby causing lithium ions to move through the aqueous lithium saltsolutions 340 a, 340 b, respectively, through the lithium ion-selectivemembranes 350 a, 350 b, respectively, travel to the surface of theconductive substrate 310, where each lithium ion gains an electron,thereby electrodepositing the layers of elemental lithium 360 a, 360 bonto the first side and the second side, respectively, of the conductivesubstrate 310, the layers of elemental lithium 360 a, 360 b thus formingand bonding to the conductive substrate 310 and, respectively, to thelithium ion-selective membranes 350 a, 350 b. In this manner, as shownin FIGS. 10 and 11, the double-sided lithium metal electrode 315 ismanufactured as a sandwich with a central conductive substrate 310bounded on opposite sides by layers of elemental lithium 360s, 360 b,the layers of elemental lithium 360 a, 360 b in turn bounded by layersof lithium ion-selective membrane 350 a, 350 b. During the process ofelectrodeposition, the conductive substrate 310 is stationary in theelectrolytic cell.

In some embodiments, the first and second chambers 326 a, 326 b of theelectrolytic cell 305 of FIGS. 10 and 11 are flow chambers, withentrance ports 370 a, 370 b and exit ports 380 a, 380 b allowing aqueouslithium salt solutions 340 a, 340 b to enter the first chamber 326 a andthe second chamber 326 b to provide a renewable supply of lithium ionsfor electrodepositing.

In preferred embodiments, the constant current is between about 10mA/cm² and about 50 mA/cm². In preferred embodiments, the constantcurrent applied is about 25 mA/cm² to about 50 mA/cm². In preferredembodiments, the constant current applied is about 40 mA/cm² to about 50mA/cm². In preferred embodiments, the constant current is applied for atime between about 1 minute and about 60 minutes.

In preferred embodiments, the aqueous lithium salt solution 340 a, 340 bis selected from the group consisting of Li₂SO₄, Li₂CO₃, andcombinations thereof. In preferred embodiments, the aqueous lithium saltsolution 340 a, 340 b includes Li₂SO₄. In preferred embodiments, thelithium ion selective membrane 350 a, 350 b comprises a polymeric matrixand a plurality of ion-conducting particles disposed within thepolymeric matrix. In a preferred embodiment, the lithium ion selectivemembrane 350 a, 350 b includes a glass frit with lithium ion conductingparticles disposed within.

In an alternative method of manufacturing by electrodeposition thedouble-sided lithium electrode 315 of the galvanic cell 325 of FIG. 9,the electrolytic cell 105 of FIG. 5 is used. According to this method,the lithium ion selective membranes 150 a, 150 b and the conductivesubstrate 110 each remain stationary in the electrolytic cell. Avariable voltage is applied across the positive electrodes 120 a, 120 band the conductive substrate 110 of the electrolytic cell 105, in orderto maintain a constant current, thereby causing lithium ions to movethrough the aqueous lithium salt solutions 140 a, 140 b, cross from thefirst and fourth chambers 126 a, 126 b to the second and third chambers128 a, 128 b, respectively, through the lithium ion selective membranes150 a, 150 b, into the non-aqueous electrolytes 130 a, 130 b, travel tothe first and the second faces of the conductive substrate 110, whereeach lithium ion gains an electron, thereby causing layers of elementallithium 160 a, 160 b to be electrodeposited on the conductive substrate110. As the layers of elemental lithium 160 a, 160 b grow, they displacenon-aqueous electrolytes 130 a, 130 b from the second and third chambers128 a, 128 b, respectively, eventually coming into contact with andbonding to the lithium ion selective membranes 150 a, 150 b, therebyforming the double-sided lithium metal electrode 315 of FIG. 9,comprising the conductive substrate 110 and the layers of lithium 160 a,160 b, wherein the layers of lithium 160 a, 160 b are bonded,respectively on the first and second faces of the conductive substrate110 and to the lithium ion-selective membranes 150 a, 150 b, wherein thelithium ion-selective membranes 150 a, 150 b, are configured to functionas solid state electrolytes.

In preferred embodiments, the lithium metal electrodes described hereincan be integrated into batteries, including but not limited to thebatteries embodied in FIGS. 6 and 9.

The methods described above are well-suited for vertically integratedbattery production, thereby allowing for a supply chain for LMBproduction that is regionally controlled in any region where lithium ismined (for example, in the US). The development of such a local regionalsupply chain greatly reduces costs, and provides LMBs that areinherently cobalt free.

A typical fabrication facility for lithium ion batteries according tothe prior art is shown in FIG. 12. Manufacturing stages involvefabrication of anodes 401 and cathodes 403, cell assembly and cellfinishing and testing. Anodes 401 and cathodes 403 follow paralleltracks involving mixing 402 to form a slurry, coating 404 ontoconductive foil, pressing 406 to bond coating to foil, and slitting 408to form desired electrode dimensions. Following roll formation 410,cells are assembled 420, filled with electrolyte and sealed 430. BecauseLIB cells are manufactured in a fully discharged state, the final stageof the process involves cell finishing, a time-consuming that mayinclude steps of charge and discharge 440, degassing and final sealing450, further charge and discharge 460 and finally aging 480. Because ofthe multiple, time-consuming steps, the finishing process can takebetween 20-30 days.

According to the embodiments described above, lithium metal electrodescan be fabricated in situ, thereby providing lithium metal anodes forLMBs in a fully charged state. According to the embodiment of FIG. 13,the processes described above for lithium metal anode fabrication can bevertically integrated into a cost- and energy-efficient manufacturingmethod for LMBs. As embodied in FIG. 13, the cathode 403 is stillmanufactured by conventional methods involving mixing 402, coating 404,and pressing 406. However, the working anode is now formed byelectrolysis 405 according to the process embodied in FIG. 1, involvingblanketing an electrolytic cell with a blanketing atmosphere 2, applyingconstant current to the cell 4, flowing Li⁺ across a lithium selectivemembrane 6, reducing Li⁺ to Li metal 8, and fabricating a Li metalbattery 12, by steps involving pouch formation 412, cell assembly 420,cell filling and sealing 430, and finishing steps 490. Cell assembly 420includes the steps of assembling a casing with contents including theworking anode, and other components to form a lithium metal battery, andsealing the casing to isolate the contents from reactants present in theair.

As embodied in FIG. 13, LMB manufacture according to the currentinvention is a vertically integrated process that replaces the anodefabrication process by an in situ low-temperature electrodepositionprocess, utilizing as feedstock an aqueous lithium salt solution, wherethe electrodeposition occurs through a lithium ion selective membrane toproduce a highly pure lithium metal anode, resistant to dendriteformation. Because lithium metal negative electrodes are fabricated in afully charged state, the lengthy formation process required for lithiumion batteries is not required.

Because of the use of the lithium ion selective membrane, and the highcurrent densities, a relatively inexpensive impure feed such as Li₂SO₄can be used for electrodeposition, saving energy and reducing costs.Impurities in the lithium metal anodes are further reduced by performingthe electrodeposition entirely in a blanketing atmosphere, substantiallydepleted of lithium reactive components including nitrogen, oxygen,ozone, oxides of nitrogen, sulfur and phosphorous, carbon dioxide,halogens, hydrogen halides, and water. In preferred embodiments, theinert atmosphere is purified argon gas. In some embodiments, stepsfollowing electrodeposition, including cell assembly, electrolyte/cellfilling and sealing are also performed in the inert atmosphere. In otherembodiments, only the lithium electrodeposition occurs under inertatmosphere, with remainder of battery manufacturing processes takingplace in “dry air,” where dry air refers to air with less than 1% RH(relative humidity) (−45° C. dew point). In preferred embodiments,during LMB manufacture the temperature is kept between about 20° C. andabout 30° C. In preferred embodiments, during LMB manufacture thetemperature is kept between about 23° C. and about 27° C.

A variety of different LMB battery configurations are understood to beencompassed by the invention described above. FIG. 14 embodies asingle-cell battery configuration 14, shown as manufactured with abattery case, showing electrical contacts to the anode 245 and to thecathode 255. FIG. 15 embodies a double-cell battery configuration 16, asmanufactured with a battery case, showing a single electrical contact tothe anode 245, and two electrical contacts 255 a, 255 b, to the cathode.

The embodiments of the invention described above are intended to bemerely exemplary; numerous variations and modifications will be apparentto those skilled in the art. All such variations and modifications areintended to be within the scope of the present invention as defined inany appended claims.

1. A method of manufacturing a lithium electrode, comprising: (1)providing an electrolytic cell, the electrolytic cell including: a firstchamber containing a positive electrode, and an aqueous lithium saltsolution in contact with the positive electrode; a second chambercontaining a conductive substrate configured as a negative electrode,the conductive substrate being stationary in the chamber during lithiummetal electrodeposition, a lithium ion selective membrane separating thefirst chamber from the second chamber, and a non-aqueous electrolytedisposed between the conductive substrate and the lithium ion selectivemembrane, physically contacting both the conductive substrate and thelithium ion selective membrane; the electrolytic cell being configuredto allow passage of lithium ions through the lithium ion selectivemembrane between the first and the second chambers, and to precludepassage of other chemical species between the first and the secondchambers; (2) blanketing the electrolytic cell with a blanketingatmosphere, the blanketing atmosphere being substantially free oflithium reactive components; (3) applying a variable voltage in order tomaintain a constant current across the negative electrode and thepositive electrode, thereby causing lithium ions to cross from the firstchamber to the second chamber, through the lithium ion selectivemembrane and the non-aqueous electrolyte, and electrodeposit a firstlayer of lithium onto the conductive substrate, thereby forming thelithium electrode, the first layer of lithium having an inner face andan outer face, the inner face of the first layer of lithium bonded tothe conductive substrate; wherein the constant current is between about10 mA/cm² and about 50 mA/cm², and wherein the constant current isapplied for a time between about 1 minute and about 60 minutes.
 2. Themethod according to claim 1, wherein the blanketing atmosphere includesno more than 10 ppm of lithium reactive components on a molar basis. 3.The method according to claim 1, wherein the blanketing atmosphereincludes no more than 10 ppm nitrogen on a molar basis.
 4. The methodaccording to claim 1, wherein the blanketing atmosphere includes no morethan 5 ppm nitrogen on a molar basis.
 5. The method according to claim1, wherein the conductive substrate comprises a plate having a firstface and a second face, wherein the inner face of the first layer oflithium metal bonds to the first face of the conductive substrate. 6.The method according to claim 1, wherein the aqueous lithium saltsolution comprises a lithium salt selected from the group consisting ofLi₂SO₄, Li₂CO₃, and combinations thereof.
 7. The method according toclaim 1, wherein the aqueous lithium salt solution includes Li₂SO₄. 8.The method according to claim 1, wherein the conductive substrate isselected from a group consisting of copper, aluminum, graphite coatedcopper, and nickel.
 9. The method according to claim 1, wherein thelithium ion selective membrane comprises a polymeric matrix and aplurality of ion-conducting particles disposed within the polymericmatrix.
 10. The method according to claim 1, wherein the lithium ionselective membrane comprises a glass frit with lithium ion conductingparticles disposed within.
 11. The method according to claim 1, whereinthe atmosphere comprises argon with a purity of greater than 99.998weight percent.
 12. The method according to claim 1, wherein the lithiumelectrode has a specific capacity of greater than about 3800 mAh pergram of lithium.
 13. A method of manufacturing a lithium electrode,comprising: (1) providing a gas-impermeable container, the containerenclosing: a blanketing atmosphere, the blanketing atmosphere beingsubstantially free of lithium reactive components; an electrolytic cell,the electrolytic cell being blanketed completely by the blanketingatmosphere, and including: a conductive substrate, stationary within thecell, configured as a negative electrode; a positive electrode; anaqueous lithium salt solution interposed between the conductivesubstrate and the positive electrode; a lithium ion-selective membraneconfigured to function as a solid state electrolyte, covering theconductive substrate, and forming a barrier separating the aqueouslithium salt solution and the conductive substrate; the electrolyticcell being configured to allow passage of lithium ions from the lithiumsalt solution through the lithium ion selective membrane and onto thesurface of the conductive substrate, and to preclude the passage ofother chemical species; (2) applying a variable voltage in order tomaintain a constant current across the negative electrode and thepositive electrode, thereby causing lithium ions to cross from thelithium salt solution through the lithium ion selective membrane, andelectroplate a layer of lithium onto the conductive substrate, therebyforming the lithium electrode, the layer of lithium having an inner faceand an outer face, the inner face bonding to the conductive substrateand the outer face bonding to the lithium ion-selective membrane;wherein the constant current is between about 10 mA/cm² and about 50mA/cm², and wherein the constant current is applied for a time betweenabout 1 minute and about 60 minutes.
 14. A method of manufacturing alithium metal battery, comprising: manufacturing a lithium electrodeaccording to the method of claim 1; assembling a casing with contentsincluding the lithium electrode configured as an anode, and othercomponents necessary to form the lithium metal battery; sealing thecasing to isolate the contents of the casing from reactants present inair, thereby providing the lithium metal battery.
 15. The method ofmanufacturing according to claim 14, the method being performed in asingle manufacturing facility.
 16. A method of manufacturing a lithiummetal battery, comprising: manufacturing a lithium electrode accordingto the method of claim 13; assembling a casing with contents includingthe lithium ion selective electrode configured as an anode, and othercomponents necessary to form the lithium metal battery; sealing thecasing to isolate the contents of the casing from reactants present inair, thereby providing the lithium metal battery.
 17. The method ofmanufacturing according to claim 16, the method being performed in asingle manufacturing facility.
 18. The method of manufacturing accordingto claim 17, the method being performed entirely under an atmosphereinert to chemical reaction with lithium.
 19. A method of manufacturing alithium metal battery, comprising: manufacturing a lithium metalelectrode comprising a conductive substrate and a layer of lithium metalbonded to the conductive substrate, wherein the layer of lithium metalincludes no more than 5 ppm of non-metallic elements by mass; assemblinga casing with contents including the lithium metal electrode configuredas an anode, and other components necessary to form the lithium metalbattery; sealing the casing to isolate the contents of the casing fromreactants present in air, thereby providing the lithium metal battery.20. The method of manufacturing according to claim 19, the method beingperformed in a single manufacturing facility.
 21. The method ofmanufacturing according to claim 20, the method being performed entirelyunder an atmosphere inert to chemical reaction with lithium.
 22. Amethod of manufacturing a lithium electrode, comprising: (1) providingan electrolytic cell, the electrolytic cell including: a conductivesubstrate, stationary within the electrolytic cell, the conductivesubstrate comprising a plate having a first face and a second face; afirst chamber containing a first positive electrode, and a first aqueouslithium salt solution in contact with the first positive electrode; asecond chamber containing a first lithium ion-selective membraneseparating the first chamber from the second chamber, and a firstnon-aqueous electrolyte disposed between the first face of theconductive substrate and the first lithium ion selective membrane,physically contacting both the first face of the conductive substrateand the first lithium ion selective membrane; a third chamber containinga second lithium ion-selective membrane and a non-aqueous electrolytedisposed between the second face of the conductive substrate and thesecond lithium ion selective membrane, physically contacting both thesecond face of the conductive substrate and the second lithium ion afourth chamber containing a second positive electrode, and a secondaqueous lithium salt solution in contact with the second positiveelectrode; the second lithium ion-selective membrane separating thethird chamber from the fourth chamber; the electrolytic cell beingconfigured to allow passage of lithium ions through the first lithiumion selective membrane between the first and the second chambers, and topreclude passage of other chemical species between the first and thesecond chambers; the electrolytic cell being configured to allow passageof lithium ions through the second lithium ion selective membranebetween the fourth and the third chambers, and to preclude passage ofother chemical species between the fourth and the third chambers; (2)blanketing completely the electrolytic cell with a blanketingatmosphere, the blanketing atmosphere being inert to chemical reactionwith lithium; (3) applying a variable voltage in order to maintain aconstant current across the conductive substrate and the first positiveelectrode, and across the conductive substrate and the second positiveelectrode, thereby causing lithium ions to cross from the first chamberto the second chamber, through the first lithium ion selective membraneand the first non-aqueous electrolyte, and electroplate a first layer oflithium onto the first face of the conductive substrate, and furthercausing lithium ions to cross from the fourth chamber to the thirdchamber, through the second lithium ion selective membrane and thesecond non-aqueous electrolyte, and electroplate a second layer oflithium onto the second face of the conductive substrate, therebyforming the lithium electrode, the lithium electrode comprising theconductive substrate, the first layer of lithium, and the second layerof lithium, the first layer of lithium having an inner face and an outerface, the inner face bonded to the first face of the conductivesubstrate, the second layer of having an inner face and an outer face,the inner face bonded to the second face of the conductive substrate;wherein the constant current is between about 10 mA/cm² and about 50mA/cm², and wherein the constant current is applied for a time betweenabout 1 minute and about 60 minutes.
 23. A method of manufacturing alithium electrode, comprising: (1) providing an electrolytic cell, theelectrolytic cell including: a conductive substrate, stationary withinthe cell, the conductive substrate comprising a plate having a firstface and a second face, the first face covered with a first lithiumion-selective membrane, and the second face covered with a secondlithium ion-selective membrane, the first and second lithiumion-selective membranes configured to function as solid stateelectrolytes; a first chamber containing a first positive electrode, anda first aqueous lithium salt solution in contact with the first positiveelectrode and with the first lithium ion-selective membrane; a secondchamber containing a second positive electrode, and a second aqueouslithium salt solution in contact with the first positive electrode andwith the second lithium ion-selective membrane; the electrolytic cellbeing configured to allow passage of lithium ions through the firstlithium ion selective membrane between the first chamber and the firstface of the conductive substrate, and to preclude passage of otherchemical species between the first chamber and the first face of theconductive substrate; the electrolytic cell being configured to allowpassage of lithium ions through the second lithium ion selectivemembrane between the second chamber and the second face of theconductive substrate, and to preclude passage of other chemical speciesbetween the second chamber and the second face of the conductivesubstrate; (2) blanketing completely the electrolytic cell with ablanketing atmosphere, the blanketing atmosphere being inert to chemicalreaction with lithium; (3) applying a variable voltage in order tomaintain a constant current across the conductive substrate and thefirst positive electrode, and across the conductive substrate and thesecond positive electrode, thereby causing lithium ions to cross fromthe first chamber through the first lithium ion selective membrane, andelectroplate a first layer of lithium onto the first face of theconductive substrate, and further causing lithium ions to cross from thesecond chamber through the second lithium ion selective membrane, andelectroplate a second layer of lithium onto the second face of theconductive substrate, thereby forming the lithium electrode, the lithiumelectrode comprising the conductive substrate, the first layer oflithium, and the second layer of lithium, the first layer of lithiumhaving an inner face and an outer face, the inner face of the firstlayer of lithium bonded to the first face of the conductive substrate,and the outer face of the first layer of lithium bonded to the firstlithium ion-selective membrane, the second layer of lithium having aninner face and an outer face, the inner face of the second layer oflithium bonded to the second face of the conductive substrate, and theouter face of the second layer of lithium bonded to the second lithiumion-selective membrane; wherein the constant current is between about 10mA/cm² and about 50 mA/cm², and wherein the constant current is appliedfor a time between about 1 minute and about 60 minutes.
 24. The methodaccording to claim 1, wherein the lithium ion selective membrane isstationary in the electrolytic cell, and wherein as the first layer oflithium is formed, the first layer of lithium displaces non-aqueouselectrolyte from a space between the conductive substrate and thelithium ion-selective membrane, thereby bonding the inner face of thefirst layer of lithium to the conductive substrate and the outer face ofthe first layer of lithium to the ion selective membrane, therebyforming a lithium metal electrode comprising the conductive substrateand the first layer of lithium metal, with the inner face of the firstlayer of lithium bonded to the conductive substrate, and the outer faceof the first layer of lithium bonded to the lithium ion-selectivemembrane, which is configured to function as a solid state electrolytewhen the lithium metal electrode is incorporated into a galvanic cell.25. The method according to claim 24 wherein the first and the secondlithium ion selective membranes are immovable in the electrolytic cell,and wherein as the first layer of lithium is formed, the first layer oflithium displaces the first non-aqueous electrolyte from the spacebetween the first face of the conductive substrate and the first lithiumion-selective membrane, thereby bonding the inner face of the firstlayer of lithium to the first face of the conductive substrate and theouter face of the first layer of lithium to the first lithium ionselective membrane, and wherein as the second layer of lithium isformed, the second layer of lithium displaces the second non-aqueouselectrolyte from the space between the second face of the conductivesubstrate and the second lithium ion-selective membrane, thereby bondingthe inner face of the second layer of lithium to the second face of theconductive substrate and the outer face of the second layer of lithiumto the second lithium ion-selective membrane, thereby forming a lithiummetal electrode comprising the conductive substrate and the first andsecond layers of lithium metal, with the inner face of the first layerof lithium bonded to the first face of the conductive substrate, and theouter face of the first layer of lithium bonded to the first lithiumion-selective membrane, and further with the inner face of the secondlayer of lithium bonded to the second face of the conductive substrate,and the outer face of the second layer of lithium bonded to the secondlithium ion-selective membrane, wherein the first and second lithiumion-selective membranes are configured to function as solid stateelectrolytes when the lithium metal electrode is incorporated into agalvanic cell.